Unconventional Pathway in the Gas-Phase Synthesis of 9H-Fluorene (C 13 H 10 ) via the Radical-Radical Reaction of Benzyl (C 7 H 7 ) with Phenyl (C 6 H 5 ).

The simplest polycyclic aromatic hydrocarbon (PAH) carrying a five-membered ring-9H-fluorene (C 13 H 10 )-is produced isomer-specifically in the gas phase by reacting benzyl (C 7 H 7 ⋅) with phenyl (C 6 H 5 ⋅) radicals in a pyrolytic reactor coupled with single photon ionization mass spectrometry. The unconventional mechanism of reaction is supported by theoretical calculations, which first produces diphenylmethane and unexpected 1-(6-methylenecyclohexa-2,4-dienyl)benzene intermediates (C 13 H 12 ) accessed via addition of the phenyl radical to the ortho position of the benzyl radical. These findings offer convincing evidence for molecular mass growth processes defying conventional wisdom that radical-radical reactions are initiated through recombination at their radical centers. The structure of 9H-fluorene acts as a molecular building block for complex curved nanostructures like fullerenes and nanobowls providing fundamental insights into the hydrocarbon evolution in high temperature settings.